EP1078976A1 - Procédé de production d'huiles ayant un indice de viscosité élevé - Google Patents

Procédé de production d'huiles ayant un indice de viscosité élevé Download PDF

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Publication number
EP1078976A1
EP1078976A1 EP00402205A EP00402205A EP1078976A1 EP 1078976 A1 EP1078976 A1 EP 1078976A1 EP 00402205 A EP00402205 A EP 00402205A EP 00402205 A EP00402205 A EP 00402205A EP 1078976 A1 EP1078976 A1 EP 1078976A1
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EP
European Patent Office
Prior art keywords
approximately
catalyst
metal
mass
oils
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EP00402205A
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German (de)
English (en)
French (fr)
Inventor
Patrick Briot
Christophe Gueret
Jean-Claude Hipeaux
Eric Benazzi
Pierre Marion
Alain Billon
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only

Definitions

  • the subject of the present invention is a process for obtaining oils having viscosity indices high, and more particularly viscosity indices higher than about 100, from a charge containing constituents with boiling points above 300 ° C.
  • the process is a sequence of operations, allowing the recovery of an oily residue which is partly fractionated by thermal diffusion, into different oils of compositions and viscosity indices different.
  • WO 97/18278 describes a process for producing dewaxed lubricating oil, comprising at least one hydrocracking zone, at least one dewaxing zone and at least a hydrorefining zone.
  • the hydrocarbon feedstock includes first gas oils vacuum distillation, deasphalted raffinates or a mixture of two of these cuts. Charges crackles may also be added to the initial charge, but in amounts not exceeding 20 %, due to their high aromatic content and their low hydrogen content.
  • US Patent 4,975,177 describes a process in three successive stages, for the production of lubricant viscosity index of at least 130 and pour point less than 5 ° F, (-15 ° C) comprising a dewaxing step from an oil charge to form a filler rich in paraffin containing at least 50% by mass of paraffin and having a point boiling above 650 ° F (343 ° C), a catalytic dewaxing step by isomerization effluent obtained in step a), at high pressure, in the presence of hydrogen and a catalyst containing a beta zeolite and a hydro-dehydrogenating function, in order to isomerize the n-paraffins in iso-paraffins, as well as a selective dewaxing step, in the presence of a zeolite catalyst having a stress index of at least 8.
  • the presence of hydrogen in the second step maintains the activity of the catalyst and promotes the different stages of the isomerization mechanism. Isomerization then leads to hydrogenation
  • Patent FR 2 600 669 of the applicant describes a hydrocracking process in three stages successive intended for the production of middle distillates (petrol, kerosene and diesel), which allows collect fractions according to their boiling points. So the fractions of boiling points below 375 ° C are recovered and those with boiling points above 375 ° C are recycled.
  • middle distillates petrol, kerosene and diesel
  • the present application is based on the recovery of oily fractions according to their viscosity indices. On the other hand, it allows to recover, not only middle distillates but still a bottom product containing essentially oils of composition and of different viscosity indices.
  • the object of the invention is the production of oils with high viscosity indices, preferably greater than about 100, and even more preferably greater than about 140, by direct processing of petroleum fractions.
  • One of the advantages of the invention is the obtaining of oils of different compositions.
  • the refiner has the choice between recovering the oils or recycling them, according to the limit viscosity index that it has set.
  • the invention relates more particularly to a process for producing oils having a high viscosity index, and applies to a feed containing constituents with boiling points above 300 ° C.
  • the fillers used in the context of the present invention are petroleum fractions with boiling points above 300 ° C, usually between about 300 and 650 ° C, preferably between about 350 and 550 ° C. These charges are of various origins.
  • said feedstocks come either from crude oil distillates or from effluents from conversion units such as, for example, catalytic cracking units in a fluidized bed, hydrocracking or hydrotreating in bubbling bed.
  • These fillers mainly contain aromatic, naphthenic and paraffinic compounds. They are characterized by defined kinematic viscosities, according to standard standards at 40 and 100 ° C.
  • the kinematic viscosity at 40 ° C is usually between about 40 and 500 square millimeters per second (mm 2 / s), most often between about 40 and 300 mm 2 / s and the kinematic viscosity at 100 ° C, is generally between between about 2 and 40 mm 2 / s, most often between about 5 and 15 mm 2 / s at 15 ° C.
  • the fillers usually have a density of between about 0.89 and 0.98, most often between about 0.91 and 0.97 at 15 ° C.
  • the process according to the invention is a process for producing oils having a viscosity index high, from a charge containing constituents with boiling points greater than about 300 ° C. It includes a step a) in which hydrogen is reacted with the charge or with mixing the charge with at least a fraction of a recycling stream from step c), presence of a catalyst comprising at least one non-zeolitic amorphous matrix and at least a metal or metal compound from group VIII of the periodic table and / or at least one metal from group VI.B, a step b) in which at least part is fractionated of the effluent obtained in step a) so as to separate at least one residue of oils containing in majority of constituents with higher viscosity indices than that of the filler, and a step c) in which at least part of the oil residue is fractionated by thermal diffusion obtained in step b) in fractions of oils having high viscosity indices. Said process allows the oils to be separated according to their viscosity index.
  • step a) the charge is converted into at least one effluent containing mainly kerosene, gasoline, diesel and oils.
  • the catalyst of the first stage can be in the form of balls, but it is most often in extruded form.
  • the hydro-dehydrogenating function of said catalyst is provided by the metal or metal compound chosen from the group formed by the metals of group VIII of the classification periodic of the elements (nickel and cobalt in particular), and the metals of group VI.B (molybdenum and tungsten in particular). It is also possible to combine at least one metal from group VIII (nickel and / or cobalt) with at least one metal from group VI.B (molybdenum and / or tungsten).
  • the total concentration of the elements of groups VIII and VI.B is expressed by their concentration of metal oxides.
  • the concentration of group VIII metal oxides is usually between approximately 0.5 and 10% by mass and preferably between approximately 1 and 7% by mass.
  • the concentration of group VI.B metal oxides is usually between approximately 1 and 30% by mass, and preferably between approximately 5 and 20% by mass.
  • the total concentration of metal oxides of groups VI.B and VIII is usually between approximately 5 and 40% by mass, and most often between approximately 7 and 30% by mass.
  • the mass ratio expressed as metal oxides between metal (or metals) of group VI over metal (or metals) of group VIII is generally about 20 to 1 and most often about 10 to 2.
  • the catalyst matrix of step a) is usually chosen from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals.
  • an ⁇ or ⁇ alumina matrix is used.
  • the matrix can also contain oxides chosen from the group formed by boron oxide, zirconia, titanium oxide and phosphoric anhydride. Most often, the matrix is doped with phosphorus and possibly boron.
  • the presence of phosphorus in the catalyst makes it possible on the one hand to facilitate the preparation, in particular during the impregnation of the nickel and molybdenum solutions, and on the other hand, to improve the acidity and the hydrogenation activity of the catalyst.
  • the concentration of phosphoric anhydride P 2 O 5 is usually less than approximately 20% by mass, more often less than approximately 10% and even more preferably less than approximately 1% by mass.
  • the concentration of boron trioxide B 2 O 3 is usually less than about 10% by mass.
  • the hydrogen used in step a) of the process according to the invention essentially serves to hydrogenate aromatic compounds contained in the feed.
  • the catalyst of step a) promotes hydrogenation over cracking. It allows the opening naphthenic rings and the hydrogenation of aromatic compounds, in order to reduce the content into condensed polycyclic aromatic hydrocarbons. This reduction translates into a decrease of the effluent density, as well as an increase in its paraffinic carbon content and its viscosity index. In addition, most of the nitrogen products contained in the feed are also transformed.
  • the catalyst of step a) makes it possible to promote the transformation of sulfur sulfur compounds and nitrogen compounds in the form of ammonia. The load conversion remains limited. Most often, it remains less than or equal to about 50 % by mass, in step a) of the process of the invention.
  • the effluent obtained in step a) can be fractionated in at least one separator, into at least one gaseous effluent, and at least one liquid effluent.
  • the gaseous effluent mainly contains hydrogen sulfide, ammonia and light hydrocarbons of 1 to 4 carbon atoms. The more often, the separation requires a high pressure separator, making it possible to eliminate the effluent which is evacuated.
  • the light hydrocarbons which are recovered can be used in the fuel-gas network.
  • Step a) can be followed by a hydrocracking step d), which brings at least one part of the total effluent obtained in step a) or part of the liquid effluent obtained after fractionation, with hydrogen, in the presence of a catalyst comprising at least one zeolite, at least one matrix, and at least one metal or compound of metal from group VIII of the periodic classification of the elements and / or at least one metal from group VI.B, said metal having a hydro-dehydrogenating function.
  • This step d) makes it possible to improve the viscosity index of the oil residue compared to that obtained in the absence of step d).
  • Step d) is carried out when the refiner wishes to obtain very high viscosity indices.
  • a fractionation can be envisaged on the effluent from step d).
  • the separation procedure is identical to that carried out on the effluent obtained in step a).
  • the effluent obtained in step d) can thus be fractionated into at least one gaseous effluent and at least one liquid effluent.
  • the fractionation can be carried out at the end of step a), and / or at the end of step d).
  • the fractionation takes place at the end of step d) or at the end of step a) when step d) is not carried out.
  • the zeolite of the catalyst of step d) is most often an acidic zeolite HY characterized by the following specifications: a molar ratio SiO 2 / Al 2 O 3 usually between approximately 8 and 70 and preferably between approximately 12 and 40; a sodium content generally less than about 0.15% by mass, determined on the zeolite calcined at 1100 ° C; a crystalline parameter noted a, of the elementary mesh usually ranging between approximately 24.55. 10 -10 meters (m) and 24.24. 10 -10 m, preferably between about 24.38. 10 -10 and 24.26.
  • a molar ratio SiO 2 / Al 2 O 3 usually between approximately 8 and 70 and preferably between approximately 12 and 40
  • a sodium content generally less than about 0.15% by mass, determined on the zeolite calcined at 1100 ° C
  • a crystalline parameter noted a of the elementary mesh usually ranging between approximately 24.55. 10 -10 meters (m) and 24.24. 10 -10 m
  • a capacity C Na of recovery in sodium ions expressed in grams (g) of sodium per 100 g of modified zeolite, neutralized then calcined, generally greater than approximately 0.85; a specific surface area determined by the BET method usually greater than approximately 400 m 2 / g (square meter per gram) and preferably greater than approximately 550 m 2 / g; a water vapor adsorption capacity at 25 ° C for a partial pressure of 2.6 torr (or 346.63 Pa), generally greater than about 6% by mass; a porous distribution usually comprising between about 1 and 20%, preferably between about 3 and 15% of the pore volume contained in pores with a diameter between about 20. 10 -10 and 80. 10 -10 m, the rest of the pore volume being contained in pores of diameter less than 20. 10 -10 m.
  • the zeolite can optionally be doped with metallic elements such as, for example, metals of the rare earth family, in particular lanthanum and cerium, or noble metals or non-noble from group VIII of the periodic table, such as platinum, palladium, ruthenium, rhodium, iridium, iron and other metals like manganese, zinc, magnesium.
  • metallic elements such as, for example, metals of the rare earth family, in particular lanthanum and cerium, or noble metals or non-noble from group VIII of the periodic table, such as platinum, palladium, ruthenium, rhodium, iridium, iron and other metals like manganese, zinc, magnesium.
  • the weight content of zeolite is usually between about 2 and 80% and of preferably between about 3 and 50% relative to the final catalyst used in step d).
  • the catalyst matrix of step d) is a support chosen from the group formed by alumina, silica, silica-alumina, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide, clay, these compounds being used alone or in mixtures.
  • alumina support is used.
  • the hydro-dehydrogenating function is ensured by a combination of metals from groups VI.B (molybdenum and / or tungsten, in particular) and VIII (cobalt and / or nickel, in particular) of the periodic classification of the elements.
  • the catalyst can advantageously contain phosphorus, for the reasons previously mentioned in the catalyst of step a).
  • the total concentration of group VI.B. metal oxides and VIII is usually between approximately 1 and 40% by mass and preferably between approximately 3 and 30% by mass.
  • the mass ratio expressed in metal oxides, between metal (or metals) of group VI on metal (or metals) of group VIII is generally between approximately 20 and 1.25 and preferably between about 10 and 2.
  • the concentration of phosphorus oxides is usually less than about 15% by mass and preferably less than about 10% by mass.
  • the catalyst of step d) based on zeolite is more active than the catalyst of step a). So the conversion rate of step d) is higher than that of the first step. Content percentage of aromatic carbons is reduced and that in percentage of carbons paraffinics increases, which has the effect of improving the viscosity index of the effluent obtained at step d) compared to that obtained in step a).
  • the catalyst in step d) is much more sensitive to poisons than that of the first stage. It works only on currents of recycling, on total effluents obtained in step a) or on liquid effluents from a fractionation of products leaving stage a).
  • the unconverted fractions recovered in step a) or d) can be recycled at least in part. Said fractions have boiling points identical to that of the feed but with properties different chemicals. Recycling takes place either at step a) or at step d), or partially in these two steps.
  • Step b) of the method according to the invention is a step of fractionating at least part of the effluent obtained in step a) or in step d), so as to separate at least one residue of oils mostly containing constituents with higher viscosity indices than that of charge.
  • the fractionation is preferably a distillation.
  • Step c) of the process according to the invention is a fractionation step by thermal diffusion at least part of the oil residue obtained in step b) in fractions of oils having indices high viscosities, preferably greater than about 100 and even more preferably greater than about 140.
  • the oils are separated according to their viscosity index, that is to say according to their composition in aromatic, naphthenic and paraffinic carbons.
  • the viscosity index of the fractions obtained in step c) are either recycled, be recovered.
  • the choice between recycling or recovering these fractions is left to refiner.
  • the fractions having viscosity indices greater than approximately 140 are recovered.
  • These fractions are rich in paraffinic carbons.
  • the fractions of which the viscosity index is low, preferably less than about 100, constitute currents of recycling step c). This recycling is carried out either at step a) or at step d), or partially in these two steps.
  • These fractions are generally rich in aromatic carbons and poor in paraffinic carbons.
  • the acid function is provided by at least one molecular sieve, the microporous system of which has at least one main type of channel, the openings of which are formed of rings which contain 10 or 9 T atoms.
  • the T atoms are the tetrahedral atoms constitutive of the molecular sieve and can be at least one of the elements contained in the following set of atoms (Si, Al, P, B, Ti, Fe, Ga).
  • the T atoms defined above, alternate with an etal number of oxygen atoms. It is therefore equivalent to say that the openings are formed of rings which contain 10 or 9 oxygen atoms or formed of rings which contain 10 or 9 T atoms.
  • the molecular sieve used in the composition of the hydrodewaxing catalyst can also have other types of channels but whose openings are formed by rings which contain less than 10 T atoms or oxygen atoms.
  • one of the determining factors for obtaining good catalytic performance in the third stage is the use of molecular sieves having a bridge width of at most 0.75 nm, preferably between 0.50 nm and 0.75 nm, preferably between 0.52 nm and 0.73 nm.
  • the bridge width measurement is performed using a graphics and modeling tool molecular such as Hyperchem or Biosym, which builds the surface of the sieves molecular in question and, taking into account the ionic rays of the elements present in the sieve frame, measure the bridge width.
  • a graphics and modeling tool molecular such as Hyperchem or Biosym
  • the catalyst suitable for this process is characterized by a catalytic test called standard test for transformation of pure n-decane which is carried out under a partial pressure of 450 kPa of hydrogen and a partial pressure of nC 10 of 1.2 kPa, ie a pressure total of 51.2 kPa in a fixed bed and with a constant flow of nC 10 of 9.5 ml / h, a total flow of 3.6 l / h and a mass of catalyst of 0.2 g.
  • the reaction is carried out in downward flow.
  • the conversion rate is controlled by the temperature at which the reaction takes place.
  • the catalyst subjected to said test consists of pure pelletized zeolite and 0.5% mass of platinum.
  • N-decane in the presence of the molecular sieve and a hydrodehydrogenating function will undergo hydroisomerization reactions which will produce isomerized products with 10 atoms of carbon, and hydrocracking reactions leading to the formation of products containing less of 10 carbon atoms.
  • a molecular sieve used in the hydrodewaxing step according to the invention must have the physicochemical characteristics described above and lead, for a yield of isomerized products of nC 10 of the order of 5% by mass. (the conversion rate is regulated by temperature), at a 2-methylnonane / 5-methylnonane ratio greater than 5 and preferably greater than 7.
  • molecular sieves thus selected, under the conditions described above, from the numerous molecular sieves already existing, allows in particular the production of products with low pour point and high viscosity index with good yields in the context of method according to the invention.
  • zeolites that can enter into the composition of the hydrodewaxing catalyst
  • the following zeolites are catalytic: Ferrierite, NU-10, EU-13, EU-1 and zeolites of the same structural type.
  • the melocular sieves used in the composition of the catalyst hydrodewaxing are included in the set formed by ferrierite and EU-1 zeolite.
  • the mass content of molecular sieve in the hydrodewaxing catalyst is included between 1 and 90%, preferably between 5 and 90% and even more preferably between 10 and 85 %.
  • the matrices used to carry out the shaping of the catalyst are by way of examples and without limitation, alumina gels, aluminas, magnesia, amorphous silica-aluminas, and their mixtures. Techniques such as extrusion, pelletizing or coating, can be used to perform the shaping operation.
  • the catalyst also has a hydro-dehydrogenating function ensured, for example, by at least one element from group VIII and preferably at least one element included in the set formed by platinum and palladium.
  • the mass content of group VIII non-noble metal, by relative to the final catalyst, is between 1 and 40%, preferably between 10 and 30%.
  • the non-noble metal is often associated with at least one metal from group VIB (Mo and W preferred). If it is at least one noble metal from group VIII, the mass content relative to the final catalyst is less than 5%, preferably less than 3% and even more so preferred less than 1.5%.
  • platinum and / or palladium are preferably located on the matrix, defined as above.
  • the hydrodewaxing catalyst according to the invention can also contain from 0 to 20%, preferably from 0 to 10% mass (expressed as oxides) phosphorus.
  • the combination of metal (aux) of group VI B and / or of metal (s) of group VIII with phosphorus is particularly advantageous.
  • Dewaxing can be carried out either on the oil residue before step c) of fractionation by thermal diffusion, either on the non-recycled fractions withdrawn in step c).
  • the operation of dewaxing can employ a catalyst containing at least one zeolite or a solvent.
  • the paraffins obtained after solvent dewaxing can be recycled either at step a) either at step d) or partially in these two steps.
  • step a) and of step d) of the process according to the invention can be identical or different.
  • the absolute pressure is usually between approximately 2 and 35 MPa, preferably between approximately 5 and 25 MPa
  • the temperature is generally between approximately 300 and 550 ° C., preferably between 320 and 450 ° C.
  • the hourly space velocity is usually between about 0.01 and 10 h -1 , preferably between about 0.01 and 5 h -1 .
  • the H 2 / HC ratio is usually between approximately 50 and 5000 Nm 3 / m 3 , preferably between approximately 300 and 3000 Nm 3 / m 3 (normal cubic meter / cubic meter, normal signifying normal pressure conditions 0.1 MPa and a temperature of 25 ° C).
  • Step c) of the method according to the invention is carried out in at least one diffusion column thermal height usually between about 0.5 and 30 meters (m), preferably between about 0.5 and 20 m.
  • the column comprises two tubes placed one inside the other.
  • the space between the two tubes is generally between approximately 1 millimeters (mm) and 20 centimeters (cm).
  • the temperature difference between the wall of the inner tube and the wall of the outer tube is usually between about 25 and 300 ° C.
  • the inner tube wall is maintained at a temperature lower than that of the wall of the outer tube.
  • a balance thermal is established between the two walls, so that, from the head to the bottom of the column, one recovers paraffinic compounds (n and iso), monocyclic compounds (mononaphthenes and mono-aromatic), dicyclic compounds, tricyclic compounds.
  • FIGS 1 to 4 show different embodiments of the method according to the invention.
  • the charge containing constituents with boiling points greater than approximately 300 ° C is sent via line 1 to reactor 5 containing the hydrotreating catalyst and the hydrogen which comes from lines 2, 3 and 4.
  • the charge is almost completely desulfurized, and denitrogenated. It is converted into an effluent and its percentage content of aromatic carbons is reduced.
  • the effluent leaving via line 6 is sent to a high pressure separator 7 after injection.
  • wash water beforehand by a line not shown in the figure.
  • Wash water containing the ammonia and part of the dissolved hydrogen sulphide is removed from the separator by a line not shown in the figure.
  • the gases from the separator 7 contain a high content of hydrogen and are evacuated by line 8 after a possible washing allowing the elimination of hydrogen sulfide, by a line not shown in the figure.
  • Said gases contain also light hydrocarbons of 1 to 4 carbon atoms which are evacuated by line 8. Said hydrocarbons can then be used, generally after separation with hydrogen, in the fuel-gas network.
  • the remaining liquid effluent is then conveyed to a fractionation device 14 by the line 9.
  • the petrol fraction which can be used, is drawn off at the head via line 10 as catalytic reforming charge, the kerosene fraction by line 11, the diesel fraction by line 12 and at the bottom an oil residue via line 13 which is sent to a column 24 of thermal diffusion.
  • the fractions are drawn off from column 24 by lines 15 to 23.
  • the fractions drawn off by lines 15 to 19 are sent to a solvent dewaxing device 30.
  • Fractions from lines 25 to 29 have high viscosity indices.
  • the bottom product of column 24 is recycled by line 31 to load input line 1. Paraffins from dewaxing are recycled by line 32 to the reactor.
  • the embodiment of Figure 2 differs from that of Figure 1 by the device dewaxing 30 placed at the outlet of the fractionation device 14.
  • the dewaxing operation is then carried out on the oily residue.
  • This dewaxed residue is then routed via line 25 to the thermal diffusion column 24.
  • the fractions are drawn off by lines 15 to 23.
  • the fractions from lines 15 to 19 are recovered, fractions 20 to 23 are recycled by the line 26 to reactor 5.
  • the paraffins from dewaxing are recycled to reactor 5 via the line 27.
  • FIG. 3 differs from FIG. 2 by the presence of a second reactor 31, located at the outlet of the first reactor 5, containing a catalyst based on zeolite and the necessary hydrogen coming lines 3 and 4, as well as by recycling the low viscosity index fractions at the level of first and second reactor.
  • the fractions drawn off by lines 20 to 23 are recycled to the reaction system by line 26.
  • This recycling is carried out in the first reactor 5 by the line 28, and to the second reactor 31 via line 29.
  • the paraffins from dewaxing are recycled to the first reactor 5 via line 34 and to the second reactor 31 via the line 33.
  • the effluent leaving the first reactor via line 6 is conveyed to the second reactor 31 containing the hydrocracking catalyst. Under the operating conditions described above, the effluent from the first reactor 5 is transformed into an effluent containing, essentially kerosene, gasoline, diesel and an oily residue.
  • the effluent from the second reactor 31 via line 32 is sent to a high pressure separator 7, after prior injection of washing water by a line not shown in the figure.
  • the washing water containing the ammonia and part of the dissolved hydrogen sulphide is discharged from the separator, by a line not shown in the figure.
  • the gases coming from the high pressure separator 7 contain a high hydrogen content and are evacuated by line 8 after a possible washing allowing the elimination of hydrogen sulphide, by a line not shown in the figure.
  • Said gases also contain light hydrocarbons of 1 to 4 carbon atoms in their molecule and are discharged through line 8. Said hydrocarbons can then be used, after separation with hydrogen, in the fuel-gas network.
  • the liquid effluent from the high pressure separator 7 is sent via line 9 to a device 14 for fractionation. The following steps are identical to those in Figure 2.
  • the embodiment shown diagrammatically in FIG. 2 is used.
  • the charge is a petroleum distillate. Its characteristics are given in table 1.
  • the charge is sent to a reactor containing a catalyst, in the presence of hydrogen.
  • Said catalyst in the form of extrudates of 1.6 millimeters (mm) in diameter, is based on molybdenum (15% MoO 3 ), nickel (5% NiO), on a support of ⁇ alumina (80% of Al 2 O 3 ).
  • the reactor is heated to the temperature of about 390 ° C.
  • the hourly space velocity is approximately 0.5 h -1 .
  • the partial hydrogen pressure is 14.8 MPa and the H 2 / HC ratio is 1600 Nm 3 / m 3 .
  • the conversion to 375 ° C is approximately equal to 42.7% by mass. This conversion is defined by the ratio between the mass fraction of the effluent having a point boiling point below 375 ° C minus the fraction of the charge at boiling point below 375 ° C, and the fraction of the feed having a boiling point above 375 ° C.
  • the charge is then converted into an effluent containing mainly kerosene, petrol, diesel and oils.
  • the effluent from the reactor is sent to a high pressure separator to be fractionated into a gaseous effluent containing hydrogen sulfide and hydrogen, ammonia, and light hydrocarbons and which is discharged, and into an effluent liquid which is conveyed to the distillation column.
  • Different fractions from the head to the bottom of the column are collected in the following manner: a petrol fraction, a kerosene fraction, a diesel fraction and an oil residue at the bottom of the column.
  • the oil residue is dewaxed using methyl isobutyl ketone as a solvent. It is then analyzed.
  • the paraffins from dewaxing are recycled in the reactor.
  • the viscosimetric qualities of the filler and of the residue are very different.
  • the conversion being limited, the viscosity index is also reduced, while remaining equal to that currently required by customs specifications.
  • the various stages have enabled the hydrogenation of aromatic compounds and the opening of naphthenic rings, which results in a decrease in density and an increase in the viscosity index of the oil residue, compared to the initial charge.
  • Part of the residue then circulates in a thermal diffusion column, with a height of 2 meters (m) and comprising two tubes placed one inside the other.
  • the oily residue circulates in the space formed by the walls of the tubes. This space is approximately 0.25 millimeters (mm).
  • the temperature difference between the wall of the inner tube and the wall of the outer tube is about 130 ° C.
  • the thermal diffusion column has 9 racking lines, which allow the collection of residue fractions.
  • the characteristics of these fractions are given in Table 2: Number of fractions Density at 15 ° C (kg / m 3 ) Viscosity index C a (%) C p (%) C n (%) 1 828.9 168 1.6 96.7 1.7 2 837.8 147 2.0 86.3 11.6 3 849.4 140 2.6 75.6 21.8 4 857.7 127 2.9 69.5 27.6 5 876.2 103 3.7 55.4 40.8 6 892.5 76 4.5 47.5 48 7 907.0 53 5.5 49.1 45.4 8 922.7 25 6.7 45.2 48.1 9 942.2 -24 8.9 43.1 48 C a , C p and C n are the respective contents in percentages of aromatic, paraffinic and naphthenic carbons.
  • Thermal diffusion allows, from the residue of oils having a viscosity index about 98, to obtain different fractions of oils with different viscosity indices (from - 24 to 168). Different oil compositions are thus obtained.
  • the three column head fractions each have a viscosity index greater than or equal to 140. They are poor in aromatic carbons (with a content of 1.6 to 2.6%) and rich in paraffinic carbons (with a content of 76 97%).
  • the column bottom fractions (fractions 6 to 9) are rich in aromatic carbons (4.5 to 8.9%) and naphthenic carbons (45 to 48%). Their viscosity indices are less than 100. These fractions are then recycled at the level of the introduction of the charge. Depending on the choice of the refiner, fractions 4 and 5, having viscosity indices of between approximately 100 and 130, are either recycled or recovered.
  • Example 3 The same charge is used as in Example 1 but with the embodiment illustrated in the figure 3.
  • the characteristics of the load are presented in table 3.
  • the liquid effluent obtained at the outlet of the high pressure separator is introduced into a second reactor, in the presence of a second catalyst.
  • the second catalyst comprises a HY zeolite characterized by 13.6% by mass of SiO 2 , 13.49% by mass of MoO 3 , 2.93% by mass of NiO, 5.09% by mass of P 2 O 5 on a support of 64.89% by mass of Al 2 O 3 .
  • the crystalline parameter a of the elementary mesh is 24.28.10 -10 m
  • the capacity of recovery in sodium ions is 0.92
  • the specific surface determined by the BET method is 600 m 2 / g
  • the capacity of absorption of water vapor at 25 ° C for a partial pressure of 2.6 torr (346.63 Pa) is 13% by mass and the porous distribution comprises approximately 10% of the pore volume contained in pores with a diameter between 20.10 -10 m and 80.10 -10 m, the rest of the pore volume being contained in the pores with a diameter less than 20.10 -10 m.
  • the operating conditions in the second reactor are identical to those carried out in the first reactor (see example 1).
  • the effluent in output from the second reactor is sent to a high pressure separator.
  • the effluent is thus fractionated into a gaseous effluent which is discharged and into a liquid effluent.
  • the liquid effluent reaches the distillation column.
  • the viscosity index of the oil residue (equal to 129), after passing through the two successive reactors, is higher than that of the feed (equal to 34), but it is even higher than that of the residue after passing through a single reactor (equal to 98, see example 1). The same applies to the content of paraffinic carbons.
  • the viscosity indices are higher than those obtained by operating as described in Example 1. It is possible to recover fractions of oils 1 to 4, including viscosity indices between 150 and 205, as well as fractions 5 and 6 of indices between 120 and 130. Fractions 7 to 9 are recycled at the load introduction level.

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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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WO2014113195A3 (en) * 2013-01-16 2015-01-08 Exxonmobil Research And Engineering Company Liquid thermal diffusion separation of hydrocarbon fractions
WO2014113194A3 (en) * 2013-01-16 2017-01-19 Exxonmobil Research And Engineering Company Liquid thermal diffusion separation of hydrocarbon fractions
RU2790393C1 (ru) * 2022-07-04 2023-02-17 Общество с ограниченной ответственностью "ЛУКОЙЛ-Волгограднефтепереработка" Сырьевая композиция для одновременного производства основ гидравлических масел, трансформаторных масел и углеводородной основы для буровых растворов

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JP7336831B2 (ja) 2017-03-02 2023-09-01 ハイドロカーボン テクノロジー アンド イノベーション、エルエルシー ファウリングが少ない堆積物を伴う改良された沸騰床リアクター
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WO2014113195A3 (en) * 2013-01-16 2015-01-08 Exxonmobil Research And Engineering Company Liquid thermal diffusion separation of hydrocarbon fractions
WO2014113194A3 (en) * 2013-01-16 2017-01-19 Exxonmobil Research And Engineering Company Liquid thermal diffusion separation of hydrocarbon fractions
RU2790393C1 (ru) * 2022-07-04 2023-02-17 Общество с ограниченной ответственностью "ЛУКОЙЛ-Волгограднефтепереработка" Сырьевая композиция для одновременного производства основ гидравлических масел, трансформаторных масел и углеводородной основы для буровых растворов

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JP2001098281A (ja) 2001-04-10
FR2797883A1 (fr) 2001-03-02
US6783661B1 (en) 2004-08-31
KR100729285B1 (ko) 2007-06-18
KR20010096462A (ko) 2001-11-07

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